The effect of Si/Al ratio of HZSM5 zeolite-based catalysts on surface acidity and on selectivity in the transformation of methanol into hydrocarbons has been studied. The acidic strength distribution (measured by combining the differential scanning calorimetry and the chromatographic analysis) and the total acidity (measured by calorimetry and temperature programmed desorption), using ammonia and tert-butylamine, have been studied as acidity measurements. The nature of the acidic sites has been determined by FTIR analysis of both the surface OH groups and the interaction of Bronsted and Lewis sites with pyridine. The increase in light olefin selectivity and the decrease in methanol conversion with increasing Si/Al ratio are a consequence of the kinetic scheme of the reaction, which has steps in series, and can be explained by the decrease in total acidity. The same acidic sites are responsible for the formation of light olefins and for the transformation of these olefins into higher hydrocarbons.